WO2022129473A1 - A positive electrode active material for rechargeable lithium-ion batteries - Google Patents

A positive electrode active material for rechargeable lithium-ion batteries Download PDF

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Publication number
WO2022129473A1
WO2022129473A1 PCT/EP2021/086400 EP2021086400W WO2022129473A1 WO 2022129473 A1 WO2022129473 A1 WO 2022129473A1 EP 2021086400 W EP2021086400 W EP 2021086400W WO 2022129473 A1 WO2022129473 A1 WO 2022129473A1
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Prior art keywords
positive electrode
active material
electrode active
mol
material according
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PCT/EP2021/086400
Other languages
French (fr)
Inventor
Jens Martin Paulsen
Shinichi Kumakura
Liang Zhu
Jihye Kim
Jihoon Kang
Hyejeong Yang
Yuri Lee
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Umicore
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Application filed by Umicore filed Critical Umicore
Priority to JP2023536521A priority Critical patent/JP2023554416A/en
Priority to EP21839199.3A priority patent/EP4264700A1/en
Priority to KR1020237024309A priority patent/KR20230121864A/en
Priority to CN202180084544.9A priority patent/CN116601117A/en
Priority to US18/265,630 priority patent/US20240030423A1/en
Priority to CA3202635A priority patent/CA3202635A1/en
Publication of WO2022129473A1 publication Critical patent/WO2022129473A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
    • H01M4/405—Alloys based on lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/76—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by a space-group or by other symmetry indications
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a positive electrode active material for lithium-ion liquid electrolyte rechargeable batteries. More specifically, the invention relates to particulate positive electrode active materials comprising tungsten oxides.
  • This invention relates to a single-crystalline positive electrode active material powder for lithium-ion rechargeable batteries (LIBs), comprising a first compound which comprise lithium tungsten oxide, and a second compound which comprises tungsten oxide.
  • LIBs lithium-ion rechargeable batteries
  • KR 2019/0078991 discloses positive electrode active material powder comprises a mixture of lithium transition metal oxide and lithium tungsten oxide compounds.
  • the positive electrode active material according to KR 2019/0078991 has low initial discharge capacity (DQ1) and high irreversible capacity (IRRQ).
  • the positive electrode active material is a powder which comprises Li, M', and O, wherein M' consists of:
  • A in a content m superior or equal to 0 mol% and inferior or equal to 5 mol%, relative to M', whereby A comprises at least one element of the group consisting of: Al, Ba, B, Mg, Nb, Sr, Ti, W, S, Ca, Cr, Zn, V, Y, Si, and Zr,
  • Ni in a content of 100-x-y-m mol% i. a first compound which comprises U2WO4 ii. and a second compound which comprises WO3, whereby the powder is a single-crystalline powder, whereby the positive electrode active material comprises Li in a molar ratio of Li/(Co+Mn+Ni+A) of at least 0.900 and at most 1.100.
  • the present invention provides an electrochemical cell comprising a positive electrode active material according to the first aspect of the invention; a lithium ion rechargeable battery comprising a liquid electrolyte and a positive electrode active material according to the first aspect of the invention; and a use of a positive electrode active material according to the first aspect of the invention in a battery of either one of a portable computer, a tablet, a mobile phone, an electrically powered vehicle and an energy storage system.
  • Figure 1 shows an X-ray diffractogram of a positive electrode active material powder according to EX1.7 comprising U2WO4 and WO3 compounds.
  • Figure 2 shows the X-ray diffractograms of CEX2, EX1.4, and CEX3.3.
  • the horizontal axis shows the diffraction angle 20 in degrees
  • the vertical axis shows the signal intensity on a logarithmic scale.
  • “About” as used herein referring to a measurable value such as a parameter, an amount, a temporal duration, and the like, is meant to encompass variations of +/-20% or less, preferably +/-10% or less, more preferably +/-5% or less, even more preferably +/-1% or less, and still more preferably +/-0.1% or less of and from the specified value, in so far, such variations are appropriate to perform in the disclosed invention.
  • the value to which the modifier "about” refers is itself also specifically disclosed.
  • ppm parts per million on a mass basis.
  • the present invention provides a positive electrode active material, whereby the positive electrode active material is a powder which comprises Li, M', and O, wherein M' consists of:
  • A in a content m superior or equal to 0 mol% and inferior or equal to 5 mol%, relative to M', whereby A comprises at least one element of the group consisting of: Al, Ba, B, Mg, Nb, Sr, Ti, W, S, Ca, Cr, Zn, V, Y, Si, and Zr,
  • a single-crystalline powder is considered to be a powder in which 80% or more of the particles in a field of view of at least 45 pm x at least 60 pm (i.e. of at least 2700 pm 2 ), preferably of: at least 100 pm x 100 pm (i.e. of at least 10,000 pm 2 ) in a SEM image have a single-crystalline morphology.
  • a particle is considered to have single-crystalline morphology if it consists of only one grain, or a very low number of a most five, constituent grains, as observed by SEM or TEM. Contrary, a particle is considered to have a polycrystalline morphology if it consists of at least six constituent grains, as observed by SEM or TEM.
  • a positive electrode active material for lithium-ion rechargeable batteries according to the invention indeed allows a higher DQ1 and lower IRRQ. This is illustrated by examples and the results provided in the Table 2.
  • the present invention provides a positive electrode active material according to the first aspect of the invention, wherein the total content of tungsten is at least 0.20 wt.% and/or at most 2.50 wt.% with respect to the total weight of said positive electrode active material, as determined by ICP-OES analysis, whereby ICP-OES means Inductively coupled plasma - optical emission spectrometry.
  • said weight ratio is between 0.25 wt.% and 2.00 wt.% and more preferably, said weight ratio is equal to 0.30, 0.50, 1.00, 1.50, 2.00 wt.% or any value there in between.
  • a positive active material is defined as a material which is electrochemically active in a positive electrode.
  • active material it must be understood a material capable to capture and release Li ions when subjected to a voltage change over a predetermined period of time.
  • Ni content 100-x-y-m in the positive electrode active material is > 60 mol% and more preferably > 65 mol%, relative to M'.
  • Ni content 100-x-y-m in the positive electrode active material is ⁇ 95 mol% and more preferably ⁇ 90 mol%, relative to M'.
  • Mn content y in the positive electrode active material is > 0 mol% and more preferably > 5 mol%, relative to M'.
  • Mn content y in the positive electrode active material is ⁇ 35 mol% and more preferably ⁇ 30 mol%, relative to M'.
  • Co content x in the positive electrode active material is > 2 mol% and more preferably > 5 mol%, relative to M'.
  • Co content x in the positive electrode active material is ⁇ 35 mol% and more preferably ⁇ 30 mol%, relative to M'.
  • a content m in the positive electrode active material is superior or equal to 0.01 mol%, relative to M'.
  • a content m in the positive electrode active material is inferior or equal to 2.0 mol%, relative to M'.
  • the positive electrode active material has a median particle size D50 of between 2 pm and 7 pm, as determined by laser diffraction particle size analysis.
  • the positive electrode active material size D99 is at least 5 pm and at most 25 pm and more preferably is at least 7 pm and at most 20 pm, as determined by laser diffraction particle size analysis.
  • D50 and D99 each are defined herein as the particle size at 50% and 99% of the cumulative volume% distributions, respectively, of the positive electrode active material powder which may be determined by laser diffraction particle size analysis.
  • the present invention provides a positive electrode active material according to the first aspect of the invention, wherein the first compound comprises IJ2WO4 and belongs to the R-3 space group and a second compound comprises WO3 and belongs to the P21/n space group, as determined by X-Ray diffraction analysis.
  • the present invention provides a positive electrode active material according to the first aspect of the invention, wherein the total content of tungsten is between 0.20 wt.% and 2.50 wt.% with respect to the total weight of said positive electrode active material, as determined by ICP-OES analysis.
  • said weight ratio is between 0.25 wt.% and 2.00 wt.% and more preferably, said weight ratio is equal to 0.50, 1.00, 1.50, 2.00 wt.% or any value there in between.
  • the present invention provides a battery cell comprising a positive electrode active material according to the first aspect of the invention.
  • the present invention provides a use of a positive electrode active material according to the first aspect of the invention in a battery of either one of a portable computer, a tablet, a mobile phone, an electrically powered vehicle, and an energy storage system.
  • the present invention provides a positive electrode active material according to the first aspect of the invention, whereby the positive electrode active material comprises a third compound which belongs to the R-3m space group as determined by X-Ray diffraction analysis.
  • said third compound is a lithium transition metal oxide i.e. a Li-M'-oxide as defined herein above.
  • the lithium transition metal oxide is identified by X-Ray diffraction analysis. According to "Journal of Power Sources (2000), 90, 76-81", the lithium transition metal oxide has a crystal structure which belongs to the R-3m space group.
  • the present invention provides an electrochemical cell comprising a positive electrode active material according to the first aspect of the invention; a lithium ion rechargeable battery comprising a liquid electrolyte and a positive electrode active material according to the first aspect of the invention; and a use of a positive electrode active material according to the first aspect of the invention in a battery of either one of a portable computer, a tablet, a mobile phone, an electrically powered vehicle and an energy storage system.
  • the present invention provides a method for preparing a positive electrode active material according to the first aspect of the invention, as described herein above, wherein the method comprises the following steps of: mixing a single-crystalline lithium transition metal oxide powder with a W containing compound so as to obtain a mixture, heating the mixture in an oxidizing atmosphere at a temperature of between 250°C and 450°C so as to obtain the positive electrode active material.
  • the W containing compound is WO3.
  • the amount of W used is in said process is between 0.20 wt.% and 2.50 wt.% with respect to the total weight of said positive electrode active material, as determined by ICP-OES analysis.
  • the second mixture is heated at a temperature of between 300°C and 400°C, and more preferably at a temperature of between 325°C and 375°C.
  • the heated powder and/or positive electrode material is further processed, for example by crushing and/or sieving.
  • the lithium transition metal oxide comprises A, wherein A comprises at least one element selected from the group consisting of: Al, Ba, B, Mg, Nb, Sr, Ti, W, S, Ca, Cr, Zn, V, Y, Si, and Zr.
  • composition of a positive electrode active material powder is measured by the inductively coupled plasma (ICP) method using an Agilent 720 ICP-OES Agilent Technologies, https ://www. agilent. com/cs/library/brochures/5990-6497EN%20720- 725_ICP-0ES_LR.pdf).
  • ICP inductively coupled plasma
  • the solution from the Erlenmeyer flask is poured into a first 250 mL volumetric flask. Afterwards, the first volumetric flask is filled with deionized water up to the 250 mL mark, followed by a complete homogenization process (1 st dilution). An appropriate amount of the solution from the first volumetric flask is taken out by a pipette and transferred into a second 250 mL volumetric flask for the 2 nd dilution, where the second volumetric flask is filled with an internal standard element and 10% hydrochloric acid up to the 250 mL mark and then homogenized. Finally, this solution is used for ICP-OES measurement.
  • the particle size distribution (PSD) of the positive electrode active material powder is measured by laser diffraction particle size analysis using a Malvern Mastersizer 3000 with a Hydro MV wet dispersion accessory (https://www.malvernpanalytical.com/en/ products/product-range/mastersizer-range/mastersizer-3000#overview) after having dispersed each of the powder samples in an aqueous medium.
  • a Malvern Mastersizer 3000 with a Hydro MV wet dispersion accessory https://www.malvernpanalytical.com/en/ products/product-range/mastersizer-range/mastersizer-3000#overview
  • D50 and D99 each are defined as the particle size at 50% and 99% of the cumulative volume% distributions obtained from the Malvern Mastersizer 3000 with Hydro MV measurements.
  • the X-ray diffraction pattern of the positive electrode active material is collected with a Rigaku X-Ray Diffractometer D/max2000 Rigaku, Du, Y., et al. (2012).
  • the instrument configuration is set at: a 1° Soller slit (SS), a 10 mm divergent height limiting slit (DHLS), a 1° divergence slit (DS) and a 0.3 mm reception slit (RS).
  • the diameter of the goniometer is 185 mm.
  • diffraction patterns are obtained in the range of 15 - 70° (29) with a scan speed of 1° per min and a step-size of 0.02° per scan.
  • a slurry that contains a positive electrode active material powder, conductor (Super P, Timcal), binder (KF#9305, Kureha) - with a formulation of 90:5:5 by weight - in a solvent (NMP, Mitsubishi) is prepared by a high-speed homogenizer.
  • the homogenized slurry is spread on one side of an aluminum foil using a doctor blade coater with a 230 pm gap.
  • the slurry coated foil is dried in an oven at 120°C and then pressed using a calendaring tool. Then it is dried again in a vacuum oven to completely remove the remaining solvent in the electrode film.
  • a coin cell is assembled in an argon-filled glovebox.
  • a separator (Celgard 2320) is located between a positive electrode and a piece of lithium foil used as a negative electrode. 1 M LiPFe in EC/DMC (1:2) is used as electrolyte and is dropped between separator and electrodes. Then, the coin cell is completely sealed to prevent leakage of the electrolyte.
  • the testing method is a conventional "constant cut-off voltage" test.
  • the conventional coin cell test in the present invention follows the schedule shown in Table 1. Each cell is cycled at 25°C using a Toscat-3100 computer-controlled galvanostatic cycling station (from Toyo).
  • the schedule uses a 1C current definition of 220mA/g.
  • the initial charge capacity (CQ1) and discharge capacity (DQ1) are measured in constant current mode (CC) at C rate of 0.1C in the 4.3 V to 3.0 V/Li metal window range.
  • the irreversible capacity IRRQ is expressed in % as follows:
  • IRRQ (%) 100*(CQl-DQl)/CQl
  • a single-crystalline positive electrode active material labelled as CEX1.1 is prepared according to the following steps:
  • Step 1) Transition metal oxidized hydroxide precursor preparation A nickel-based transition metal oxidized hydroxide powder (TMH1) having a metal composition of Ni0.86Mn0.07Co0.07 is prepared by a co-precipitation process in a large-scale continuous stirred tank reactor (CSTR) with mixed nickel manganese cobalt sulfates, sodium hydroxide, and ammonia.
  • TSH1 nickel-based transition metal oxidized hydroxide powder having a metal composition of Ni0.86Mn0.07Co0.07 is prepared by a co-precipitation process in a large-scale continuous stirred tank reactor (CSTR) with mixed nickel manganese cobalt sulfates, sodium hydroxide, and ammonia.
  • CSTR continuous stirred tank reactor
  • Step 3) First mixing: the heated powder prepared from Step 2) is mixed with LiOH in an industrial blender so as to obtain a first mixture having a lithium to metal ratio of 0.96.
  • Step 4) First firing: The first mixture from Step 3) is fired at 890°C for 11 hours in an oxidizing atmosphere so as to obtain a first fired powder.
  • Step 5) Wet bead milling: The first fired powder from Step 4) is bead milled with solid to water weight ratio of 6:4 for 20 minutes, followed by filtering, drying, and sieving process so as to obtain a milled powder.
  • Step 6) Second mixing: the milled powder from Step 5) is mixed with LiOH in an industrial blender so as to obtain a second mixture having a lithium to metal ratio of 0.99.
  • Step 7) Second firing: the second mixture from Step 6) is fired at 760°C for 10 hours in a oxidizing atmosphere, followed by crushing and sieving process so as to obtain a second fired powder labelled as CEX1.1.
  • a single-crystalline positive electrode active material labelled as CEX2 is prepared according to the following steps:
  • Step 1) Transition metal oxidized hydroxide precursor preparation A nickel-based transition metal oxidized hydroxide powder (TMH2) having a metal composition of Ni0.86Mn0.07Co0.07 is prepared by a co-precipitation process in a large-scale continuous stirred tank reactor (CSTR) with mixed nickel manganese cobalt sulfates, sodium hydroxide, and ammonia.
  • TMH2 nickel-based transition metal oxidized hydroxide powder having a metal composition of Ni0.86Mn0.07Co0.07 is prepared by a co-precipitation process in a large-scale continuous stirred tank reactor (CSTR) with mixed nickel manganese cobalt sulfates, sodium hydroxide, and ammonia.
  • CSTR continuous stirred tank reactor
  • Step 3) First mixing: the heated powder prepared from Step 2) is mixed with LiOH in an industrial blender so as to obtain a first mixture having a lithium to metal ratio of 0.96.
  • Step 4) First firing: The first mixture from Step 3) is fired at 890°C for 11 hours in an oxidizing atmosphere so as to obtain a first fired powder.
  • Step 5) Wet bead milling: The first fired powder from Step 4) is bead milled in a solution containing 0.5 mol% Co with respect to the total molar contents of Ni, Mn, and Co in the first fired powder followed by dying and sieving process so as to obtain a milled powder.
  • the bead milling solid to solution weight ratio is 6:4 and is conducted for 20 minutes.
  • Step 6) Second mixing: the milled powder obtained from Step 5) is mixed in an industrial blender with 1.5 mol% Co from CO3O4 and 7.5 mol% Li from LiOH, each with respect to the total molar contents of Ni, Mn, and Co in the milled powder so as to obtain a second mixture.
  • Step 7) Second firing: The second mixture from Step 6) is fired at 760°C for 10 hours in an oxidizing atmosphere followed by crushing and sieving process so as to obtain a second fired powder labelled as CEX2.
  • EX1.0 is prepared according to the following process:
  • Step 1) CEX1.1 is mixed with WO3 powder to obtain a mixture contains about 0.45 wt.% of tungsten with respect to the total weight of the mixture.
  • Step 2) Heating the mixture obtained from Step 1) in a furnace under the flow of an oxidizing atmosphere at 350°C for 10 hours.
  • Step 3) Crushing and sieving the heated product from Step 2) so as to obtain a powder labelled as EX1.0.
  • EX1.1 is prepared according to the following process:
  • Step 1) CEX2 is mixed with WO3 powder to obtain a mixture contains about 0.24 wt.% of tungsten with respect to the total weight of the mixture.
  • Step 2 Heating the mixture obtained from Step 1) in a furnace under the flow of an oxidizing atmosphere at 350°C for 10 hours.
  • Step 3) Crushing and sieving the heated product from Step 2) so as to obtain a powder labelled as EX1.1.
  • EX1.2, EX1.3, EX1.4, EX1.5, EX1.6, and EX1.7 are prepared according to the same method as EX1.1 except that in the Step 1) CEX2 is mixed with WO3 powder so as to obtain a mixture contains about 0.36, 0.43, 0.45, 0.48, 0.75, and 1.50 wt.% of tungsten with respect to the total weight of the mixture, respectively.
  • EX1.8 and EX1.9 are prepared according to the same method as EX1.1 except that in the Step 1) CEX2 is mixed with WO3 powder so as to obtain a mixture contains about 0.36 wt.% of tungsten with respect to the total weight of the mixture, and the heating temperature in the Step 2) are 300°C and 400°C, respectively.
  • CEX3.1 is prepared according to the same method as EX1.1 except that in the Step 1) CEX2 is mixed with WO3 powder so as to obtain a mixture contains about 3.00 wt.% of tungsten with respect to the total weight of the mixture.
  • CEX3.2 is prepared according to the same method as EX1.1 except that in the Step 1) CEX2 is mixed with WO3 powder so as to obtain a mixture contains about 0.36 wt.% of tungsten with respect to the total weight of the mixture, and no heating is applied in the Step 2).
  • CEX3.3 is prepared according to the same method as EX1.1 except that in the Step 1) CEX2 is mixed with WO3 powder so as to obtain a mixture contains about 0.45 wt.% of tungsten with respect to the total weight of the mixture, and the heating temperature applied in the Step 2) is 550°C.
  • the particle size distributions of the products from CEX1.1, CEX2, and EX1.3 were determined by a Malvern Mastersizer 3000, as described in section 1.2 above. These products all have a median particle size D50 of between 3.8 and 4.5 pm and D99 between 9.6 pm to 11.1 pm.
  • a polycrystalline positive electrode active material labelled as CEX4.1 is prepared according to the following steps:
  • Step 1) Transition metal oxidized hydroxide precursor preparation: two transition metalbased oxidized hydroxide precursors, each labelled as TMH3 and TMH4, were prepared by a co-precipitation process in a large-scale continuous stirred tank reactor (CSTR) with mixed nickel-manganese-cobalt sulfates, sodium hydroxide, and ammonia.
  • TMH3 D50 is around 10 pm and TMH4 D50 is around 4 pm, both with metal composition of Nio.65Mno.20Coo.15- Step 2)
  • TMH3 and TMH4 powders are mixed in a 7:3 ratio by weight, the lithium to metal molar ratio is 1.03, and the Zr content in the mixture is 3700 ppm.
  • Step 3) First firing: The first mixture from Step 2) is fired at 870°C for 12 hours in an oxidizing atmosphere so as to obtain a first fired powder labelled as CEX4.1.
  • CEX4.2 is prepared according to the following process:
  • Step 1) CEX4.1 is mixed with WO3 powder to obtain a mixture contains about 0.45 wt.% of tungsten with respect to the total weight of the mixture.
  • Step 2 Heating the mixture obtained from Step 1) in a furnace under the flow of an oxidizing atmosphere at 400°C for 7 hours.
  • Step 3) Crushing and sieving the heated product from Step 2) so as to obtain a powder labelled as CEX4.2.
  • a single-crystalline positive electrode active material labelled as CEX5 is prepared according to the following steps:
  • Step 1) Transition metal oxidized hydroxide precursor preparation: A nickel-based transition metal oxidized hydroxide powder (TMH5) having a metal composition of Nio.6sMno.20Coo.12 is prepared by a co-precipitation process in a large-scale continuous stirred tank reactor (CSTR) with mixed nickel manganese cobalt sulfates, sodium hydroxide, and ammonia.
  • Step 2) First mixing: TMH5 prepared from Step 1) is mixed with LiOH in an industrial blender so as to obtain a first mixture having a lithium to metal ratio of 0.97.
  • Step 4) First firing: The first mixture from Step 2) is fired at 920°C for 10 hours in an oxidizing atmosphere so as to obtain a first fired powder.
  • Step 5) Jet milling The first fired powder from Step 4) is jet milled to obtain a milled powder labelled as CEX5.
  • a single-crystalline positive electrode active material labelled as EX2 is prepared according to the following steps:
  • Step 1) CEX5 is mixed with WO3 powder to obtain a mixture contains about 0.45 wt.% of tungsten with respect to the total weight of the mixture.
  • Step 2 Heating the mixture obtained from Step 1) in a furnace under the flow of an oxidizing atmosphere at 350°C for 10 hours.
  • Step 3) Crushing and sieving the heated product from Step 2) so as to obtain a powder labelled as EX2.
  • a polycrystalline positive electrode active material labelled as CEX6.1 is prepared according to the following steps:
  • Step 1) Transition metal oxidized hydroxide precursor preparation A nickel-based transition metal oxidized hydroxide powder (TMH6) having a metal composition of Nio.soMno. Coo.io is prepared by a co-precipitation process in a large-scale continuous stirred tank reactor (CSTR) with mixed nickel manganese cobalt sulfates, sodium hydroxide, and ammonia.
  • TMG6 nickel-based transition metal oxidized hydroxide powder having a metal composition of Nio.soMno. Coo.io is prepared by a co-precipitation process in a large-scale continuous stirred tank reactor (CSTR) with mixed nickel manganese cobalt sulfates, sodium hydroxide, and ammonia.
  • CSTR continuous stirred tank reactor
  • Step 2) First heating: TMH6 prepared from Step 1) is heated at 375°C for 7 hours in an oxidizing atmosphere to obtain a heated TMH6.
  • Step 3) First mixing: heated TMH6 prepared from Step 2) is mixed with LiOH in an industrial blender so as to obtain a first mixture having a lithium to metal ratio of 1.00.
  • Step 4) Second heating: The first mixture from Step 3) is fired at 810°C for 12 hours in an oxidizing atmosphere followed by crushing and sieving process so as to obtain a fired powder labelled as CEX6.1.
  • CEX6.2 is prepared according to the following process:
  • Step 1) CEX6.1 is mixed with WO3 powder to obtain a mixture contains about 0.42 wt.% of tungsten with respect to the total weight of the mixture.
  • Step 2 Heating the mixture obtained from Step 1) in a furnace under the flow of an oxidizing atmosphere at 285°C for 8 hours.
  • Step 3) Crushing and sieving the heated product from Step 2) so as to obtain a powder labelled as CEX6.2.
  • the chemical compositions of the products from the examples and comparative examples counterexamples were determined by ICP-OES and are given in Table 2, expressed as a fraction compared to the total of Co, Ni, Mn and W.
  • Table 2 summarizes the composition of examples and comparative examples and their corresponding electrochemical properties.
  • EX1.0 shows DQ1 improvement in comparison with CEX1.1 indicating tungsten mixing and heating application according to this invention is advantageous.
  • EX1.4 shows higher DQ1 in comparison with CEX2.
  • EX1.1 to EX1.7 and CEX3.1 each comprises different tungsten content but with same heating temperature at 350°C.
  • the concentration ranges from 0.26 wt.% at EX1.1 to 1.42 wt.% at EX1.7 is demonstrated to effectively achieve the objective of this invention.
  • CEX3.1 comprising 2.92 wt.% tungsten decreases DQ1 to 196.7 mAh/g from bare CEX2 of 198.1 mAh/g.
  • EX1.8, EX1.9, CEX 3.2, and CEX3.3 show heating temperature effect to the positive electrode active material comprising tungsten source.
  • the heating temperature from 300°C at EX1.8 to 400°C at EX1.9 is demonstrated to effectively achieve the objective of this invention.
  • CEX3.2 with no heating and CEX3.3 with 550°C heating shows low DQ1 of 193.3 mAh/g and 186.5 mAh/g, respectively. This result indicates heating after tungsten mixing is essential given the temperature is lower than 550°C.
  • CEX4.1 and CEX4.2 are positive electrode active material with polycrystalline morphology comprising 65 mol% Ni.
  • CEX4.2 is further comprising 0.45 wt.% tungsten, however, shows no improvement of DQ1 in comparison with CEX4.1.
  • CEX6.1 and CEX6.2 are positive electrode active material with polycrystalline morphology comprising 80 mol% Ni wherein CEX6.2 further comprising 0.42 wt.% tungsten.
  • DQ1 for CEX6.2 in comparison with CEX6.1 It is observed that the polycrystalline morphology is not suitable to achieve the improvement in the DQ1 even with higher total Ni content in the material.
  • EX2 having a single-crystalline morphology comprising 68 mol% and 0.45 wt.% tungsten shows DQ1 improvement in comparison with CEX5 comprising the same Ni amount.
  • FIG. 1 shows the XRD patterns of EX1.7 has three phases: R-3m (a third compound phase of LiNi0.86Mn0.07Co0.07O2 according to this invention), R-3 (a first compound phase of U2WO4 according to this invention), and P21/n (a second compound phase of WO 3 ).
  • FIG. 2 shows the XRD patterns of CEX3.3, EX1.4, and CEX2.
  • CEX2 and CEX3.3 have XRD patterns related to a R-3m phase.
  • the XRD patterns indicates that CEX2 and CEX3.3 are lithium transition metal oxide compounds. They have a general formula of LiNi0.86Mn0.07Co0.07O2.
  • EX1.4 shows R-3m, R-3, and P21/n phases correspond to LiNi0.86 n0.07Co0.07O2, U2WO4, and WO3, respectively as described in Figure 1. This result indicates that 350°C heating temperature is suitable to produce the first and second compound phases according to this invention. It is when the aforementioned R-3m, R-3, and P21/n phases presence in the positive electrode active material, the electrochemical properties are improved.

Abstract

A positive electrode active material for lithium-ion liquid electrolyte rechargeable batteries, whereby the positive electrode active material is a powder which comprises Li, M', and O, wherein M' consists of Co in a content x superior or equal to 2.0 mol% and inferior or equal to 35.0 mol%, Mn in a content y superior or equal to 0 mol% and inferior or equal to 35.0 mol%, A in a content m superior or equal to 0 mol% and inferior or equal to 5 mol%, whereby A comprises at least one element of the group consisting of: Al, Ba, B, Mg, Nb, Sr, Ti, W, S, Ca, Cr, Zn, V, Y, Si, and Zr, Ni in a content of 100-x-y-m mol%, a first compound which comprises Li2WO4 and a second compound which comprises WO3, whereby the powder is a single-crystalline powder, whereby the positive electrode active material comprises Li in a molar ratio of Li/(Co+Mn+Ni+A) of at least 0.9 and at most 1.1.

Description

A POSITIVE ELECTRODE ACTIVE MATERIAL FOR RECHARGEABLE LITHIUM-ION BATTERIES
TECHNICAL FIELD
The present invention relates to a positive electrode active material for lithium-ion liquid electrolyte rechargeable batteries. More specifically, the invention relates to particulate positive electrode active materials comprising tungsten oxides.
BACKGROUND
This invention relates to a single-crystalline positive electrode active material powder for lithium-ion rechargeable batteries (LIBs), comprising a first compound which comprise lithium tungsten oxide, and a second compound which comprises tungsten oxide.
Such positive electrode active materials are already known, for example from KR 2019/0078991. The document KR 2019/0078991 discloses positive electrode active material powder comprises a mixture of lithium transition metal oxide and lithium tungsten oxide compounds. However, the positive electrode active material according to KR 2019/0078991 has low initial discharge capacity (DQ1) and high irreversible capacity (IRRQ).
It is therefore an object of the present invention to provide a positive electrode active material which has improved electrochemical properties as indicated, for example, by the DQ1 value and IRRQ value in an electrochemical cell as determined by the analytical method of the present invention.
SUMMARY OF THE INVENTION
This objective is achieved by providing a positive electrode active material for lithium-ion rechargeable batteries, whereby the positive electrode active material is a powder which comprises Li, M', and O, wherein M' consists of:
Co in a content x superior or equal to 2.0 mol% and inferior or equal to 35.0 mol%, relative to M',
Mn in a content y superior or equal to 0 mol% and inferior or equal to 35.0 mol%, relative to M',
A in a content m superior or equal to 0 mol% and inferior or equal to 5 mol%, relative to M', whereby A comprises at least one element of the group consisting of: Al, Ba, B, Mg, Nb, Sr, Ti, W, S, Ca, Cr, Zn, V, Y, Si, and Zr,
Ni in a content of 100-x-y-m mol%, i. a first compound which comprises U2WO4 ii. and a second compound which comprises WO3, whereby the powder is a single-crystalline powder, whereby the positive electrode active material comprises Li in a molar ratio of Li/(Co+Mn+Ni+A) of at least 0.900 and at most 1.100.
It is indeed observed that a higher DQ1 and a lower IRRQ is achieved using a positive electrode active material according to the present invention, as illustrated by examples and supported by the results provided in Table 2.
Further, the present invention provides an electrochemical cell comprising a positive electrode active material according to the first aspect of the invention; a lithium ion rechargeable battery comprising a liquid electrolyte and a positive electrode active material according to the first aspect of the invention; and a use of a positive electrode active material according to the first aspect of the invention in a battery of either one of a portable computer, a tablet, a mobile phone, an electrically powered vehicle and an energy storage system.
BRIEF DESCRIPTION OF THE FIGURES
By means of further guidance, a figure is included to better appreciate the teaching of the present invention. Said figure is intended to assist the description of the invention and is nowhere intended as a limitation of the presently disclosed invention.
Figure 1 shows an X-ray diffractogram of a positive electrode active material powder according to EX1.7 comprising U2WO4 and WO3 compounds.
Figure 2 shows the X-ray diffractograms of CEX2, EX1.4, and CEX3.3.
In these figures the horizontal axis shows the diffraction angle 20 in degrees, the vertical axis shows the signal intensity on a logarithmic scale.
DETAILED DESCRIPTION OF THE INVENTION
Unless otherwise defined, all terms used in disclosing the invention, including technical and scientific terms, have the meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. By means of further guidance, term definitions are included to better appreciate the teaching of the present invention. As used herein, the following terms have the following meanings:
"About" as used herein referring to a measurable value such as a parameter, an amount, a temporal duration, and the like, is meant to encompass variations of +/-20% or less, preferably +/-10% or less, more preferably +/-5% or less, even more preferably +/-1% or less, and still more preferably +/-0.1% or less of and from the specified value, in so far, such variations are appropriate to perform in the disclosed invention. However, it is to be understood that the value to which the modifier "about" refers is itself also specifically disclosed.
The recitation of numerical ranges by endpoints includes all numbers and fractions subsumed within that range, as well as the recited endpoints. All percentages are to be understood as percentage by weight, abbreviated as "wt.%" unless otherwise defined or unless a different meaning is obvious to the person skilled in the art from its use and in the context wherein it is used.
The term "ppm" is as used in this document means parts per million on a mass basis.
Positive electrode active material
In a first aspect, the present invention provides a positive electrode active material, whereby the positive electrode active material is a powder which comprises Li, M', and O, wherein M' consists of:
Co in a content x superior or equal to 2.0 mol% and inferior or equal to 35.0 mol%, relative to M',
Mn in a content y superior or equal to 0 mol% and inferior or equal to 35.0 mol%, relative to M',
A in a content m superior or equal to 0 mol% and inferior or equal to 5 mol%, relative to M', whereby A comprises at least one element of the group consisting of: Al, Ba, B, Mg, Nb, Sr, Ti, W, S, Ca, Cr, Zn, V, Y, Si, and Zr,
Ni in a content of 100-x-y-m mol%, relative to M', i. a first compound which comprises U2WO4 ii. and a second compound which comprises WO3, whereby the powder is a single-crystalline powder, whereby the positive electrode active material comprises Li in a molar ratio of Li/(Co+Mn+Ni+A) of at least 0.900 and at most 1.100. A single-crystalline powder is considered to be a powder in which 80% or more of the particles in a field of view of at least 45 pm x at least 60 pm (i.e. of at least 2700 pm2), preferably of: at least 100 pm x 100 pm (i.e. of at least 10,000 pm2) in a SEM image have a single-crystalline morphology.
A particle is considered to have single-crystalline morphology if it consists of only one grain, or a very low number of a most five, constituent grains, as observed by SEM or TEM. Contrary, a particle is considered to have a polycrystalline morphology if it consists of at least six constituent grains, as observed by SEM or TEM.
For the determination of single-crystalline morphology of particles, grains which have a largest linear dimension as observed by SEM which is smaller than 20% of the median particle size D50 of the powder as determined by laser diffraction are ignored. This avoids that particles which are in essence single-crystalline, but which may have deposited on them several very small other grains, are inadvertently considered as not having a singlecrystalline morphology.
The inventors have found that a positive electrode active material for lithium-ion rechargeable batteries according to the invention indeed allows a higher DQ1 and lower IRRQ. This is illustrated by examples and the results provided in the Table 2.
Preferably, the present invention provides a positive electrode active material according to the first aspect of the invention, wherein the total content of tungsten is at least 0.20 wt.% and/or at most 2.50 wt.% with respect to the total weight of said positive electrode active material, as determined by ICP-OES analysis, whereby ICP-OES means Inductively coupled plasma - optical emission spectrometry. Preferably, said weight ratio is between 0.25 wt.% and 2.00 wt.% and more preferably, said weight ratio is equal to 0.30, 0.50, 1.00, 1.50, 2.00 wt.% or any value there in between.
A positive active material is defined as a material which is electrochemically active in a positive electrode. By active material, it must be understood a material capable to capture and release Li ions when subjected to a voltage change over a predetermined period of time.
The content of each element can be determined by known analysis methods, such as ICP- OES (Inductively coupled plasma - optical emission spectrometry). Preferably, Ni content 100-x-y-m in the positive electrode active material is > 60 mol% and more preferably > 65 mol%, relative to M'.
Preferably, Ni content 100-x-y-m in the positive electrode active material is < 95 mol% and more preferably < 90 mol%, relative to M'.
Preferably, Mn content y in the positive electrode active material is > 0 mol% and more preferably > 5 mol%, relative to M'.
Preferably, Mn content y in the positive electrode active material is < 35 mol% and more preferably < 30 mol%, relative to M'.
Preferably, Co content x in the positive electrode active material is > 2 mol% and more preferably > 5 mol%, relative to M'.
Preferably, Co content x in the positive electrode active material is < 35 mol% and more preferably < 30 mol%, relative to M'.
Preferably, A content m in the positive electrode active material is superior or equal to 0.01 mol%, relative to M'.
Preferably, A content m in the positive electrode active material is inferior or equal to 2.0 mol%, relative to M'.
Preferably, the positive electrode active material has a median particle size D50 of between 2 pm and 7 pm, as determined by laser diffraction particle size analysis.
Preferable, the positive electrode active material size D99 is at least 5 pm and at most 25 pm and more preferably is at least 7 pm and at most 20 pm, as determined by laser diffraction particle size analysis.
D50 and D99 each are defined herein as the particle size at 50% and 99% of the cumulative volume% distributions, respectively, of the positive electrode active material powder which may be determined by laser diffraction particle size analysis.
First compound and second compound
Preferably, the present invention provides a positive electrode active material according to the first aspect of the invention, wherein the first compound comprises IJ2WO4 and belongs to the R-3 space group and a second compound comprises WO3 and belongs to the P21/n space group, as determined by X-Ray diffraction analysis.
Preferably, the present invention provides a positive electrode active material according to the first aspect of the invention, wherein the total content of tungsten is between 0.20 wt.% and 2.50 wt.% with respect to the total weight of said positive electrode active material, as determined by ICP-OES analysis. Preferably, said weight ratio is between 0.25 wt.% and 2.00 wt.% and more preferably, said weight ratio is equal to 0.50, 1.00, 1.50, 2.00 wt.% or any value there in between.
In a second aspect, the present invention provides a battery cell comprising a positive electrode active material according to the first aspect of the invention.
In a third aspect, the present invention provides a use of a positive electrode active material according to the first aspect of the invention in a battery of either one of a portable computer, a tablet, a mobile phone, an electrically powered vehicle, and an energy storage system.
Lithium transition metal oxide third compound
Preferably, the present invention provides a positive electrode active material according to the first aspect of the invention, whereby the positive electrode active material comprises a third compound which belongs to the R-3m space group as determined by X-Ray diffraction analysis.
Preferably, said third compound is a lithium transition metal oxide i.e. a Li-M'-oxide as defined herein above. The lithium transition metal oxide is identified by X-Ray diffraction analysis. According to "Journal of Power Sources (2000), 90, 76-81", the lithium transition metal oxide has a crystal structure which belongs to the R-3m space group.
Electrochemical cell
In a second aspect, the present invention provides an electrochemical cell comprising a positive electrode active material according to the first aspect of the invention; a lithium ion rechargeable battery comprising a liquid electrolyte and a positive electrode active material according to the first aspect of the invention; and a use of a positive electrode active material according to the first aspect of the invention in a battery of either one of a portable computer, a tablet, a mobile phone, an electrically powered vehicle and an energy storage system. Method for preparing a positive electrode active material
Preferably, the present invention provides a method for preparing a positive electrode active material according to the first aspect of the invention, as described herein above, wherein the method comprises the following steps of: mixing a single-crystalline lithium transition metal oxide powder with a W containing compound so as to obtain a mixture, heating the mixture in an oxidizing atmosphere at a temperature of between 250°C and 450°C so as to obtain the positive electrode active material.
Preferably, the W containing compound is WO3.
Preferably, the amount of W used is in said process is between 0.20 wt.% and 2.50 wt.% with respect to the total weight of said positive electrode active material, as determined by ICP-OES analysis.
Preferably, the second mixture is heated at a temperature of between 300°C and 400°C, and more preferably at a temperature of between 325°C and 375°C.
Preferably, the heated powder and/or positive electrode material is further processed, for example by crushing and/or sieving.
Optionally, the lithium transition metal oxide comprises A, wherein A comprises at least one element selected from the group consisting of: Al, Ba, B, Mg, Nb, Sr, Ti, W, S, Ca, Cr, Zn, V, Y, Si, and Zr.
EXAMPLES
The following examples are intended to further clarify the present invention and are nowhere intended to limit the scope of the present invention.
1. Description of analysis method
1.1. Inductively Coupled Plasma
The composition of a positive electrode active material powder is measured by the inductively coupled plasma (ICP) method using an Agilent 720 ICP-OES Agilent Technologies, https ://www. agilent. com/cs/library/brochures/5990-6497EN%20720- 725_ICP-0ES_LR.pdf). 1 gram of powder sample is dissolved into 50 mL of high purity hydrochloric acid (at least 37 wt.% of HCI with respect to the total weight of solution) in an Erlenmeyer flask. The flask is covered by a watch glass and heated on a hot plate at 380°C until the powder is completely dissolved. After being cooled to room temperature, the solution from the Erlenmeyer flask is poured into a first 250 mL volumetric flask. Afterwards, the first volumetric flask is filled with deionized water up to the 250 mL mark, followed by a complete homogenization process (1st dilution). An appropriate amount of the solution from the first volumetric flask is taken out by a pipette and transferred into a second 250 mL volumetric flask for the 2nd dilution, where the second volumetric flask is filled with an internal standard element and 10% hydrochloric acid up to the 250 mL mark and then homogenized. Finally, this solution is used for ICP-OES measurement.
1.2. Particle Size Distribution
The particle size distribution (PSD) of the positive electrode active material powder is measured by laser diffraction particle size analysis using a Malvern Mastersizer 3000 with a Hydro MV wet dispersion accessory (https://www.malvernpanalytical.com/en/ products/product-range/mastersizer-range/mastersizer-3000#overview) after having dispersed each of the powder samples in an aqueous medium. In order to improve the dispersion of the powder, sufficient ultrasonic irradiation and stirring is applied, and an appropriate surfactant is introduced. D50 and D99 each are defined as the particle size at 50% and 99% of the cumulative volume% distributions obtained from the Malvern Mastersizer 3000 with Hydro MV measurements.
1.3. X-Ray Diffraction
The X-ray diffraction pattern of the positive electrode active material is collected with a Rigaku X-Ray Diffractometer D/max2000 Rigaku, Du, Y., et al. (2012). A general method for the large-scale synthesis of uniform ultrathin metal sulphide nanocrystals. Nature Communications, 3(1)) using a Cu Ko radiation source (40 kV, 40 mA) emitting at a wavelength of 1.5418 A. The instrument configuration is set at: a 1° Soller slit (SS), a 10 mm divergent height limiting slit (DHLS), a 1° divergence slit (DS) and a 0.3 mm reception slit (RS). The diameter of the goniometer is 185 mm. For the XRD, diffraction patterns are obtained in the range of 15 - 70° (29) with a scan speed of 1° per min and a step-size of 0.02° per scan.
1.4. Coin cell test
1.4.1. Coin cell preparation
For the preparation of a positive electrode, a slurry that contains a positive electrode active material powder, conductor (Super P, Timcal), binder (KF#9305, Kureha) - with a formulation of 90:5:5 by weight - in a solvent (NMP, Mitsubishi) is prepared by a high-speed homogenizer. The homogenized slurry is spread on one side of an aluminum foil using a doctor blade coater with a 230 pm gap. The slurry coated foil is dried in an oven at 120°C and then pressed using a calendaring tool. Then it is dried again in a vacuum oven to completely remove the remaining solvent in the electrode film. A coin cell is assembled in an argon-filled glovebox. A separator (Celgard 2320) is located between a positive electrode and a piece of lithium foil used as a negative electrode. 1 M LiPFe in EC/DMC (1:2) is used as electrolyte and is dropped between separator and electrodes. Then, the coin cell is completely sealed to prevent leakage of the electrolyte.
1.4.2. Testing method
The testing method is a conventional "constant cut-off voltage" test. The conventional coin cell test in the present invention follows the schedule shown in Table 1. Each cell is cycled at 25°C using a Toscat-3100 computer-controlled galvanostatic cycling station (from Toyo).
The schedule uses a 1C current definition of 220mA/g. The initial charge capacity (CQ1) and discharge capacity (DQ1) are measured in constant current mode (CC) at C rate of 0.1C in the 4.3 V to 3.0 V/Li metal window range.
The irreversible capacity IRRQ is expressed in % as follows:
IRRQ (%) = 100*(CQl-DQl)/CQl
Table 1. Cycling schedule for coin cell testing method
Figure imgf000011_0001
2. Examples and comparative examples
Comparative Example 1
A single-crystalline positive electrode active material labelled as CEX1.1 is prepared according to the following steps:
Step 1) Transition metal oxidized hydroxide precursor preparation: A nickel-based transition metal oxidized hydroxide powder (TMH1) having a metal composition of Ni0.86Mn0.07Co0.07 is prepared by a co-precipitation process in a large-scale continuous stirred tank reactor (CSTR) with mixed nickel manganese cobalt sulfates, sodium hydroxide, and ammonia.
Step 2) Heating: the TMH1 prepared from Step 1) is heated at 400°C for 7 hours in an oxidizing atmosphere to obtain a heated powder.
Step 3) First mixing: the heated powder prepared from Step 2) is mixed with LiOH in an industrial blender so as to obtain a first mixture having a lithium to metal ratio of 0.96. Step 4) First firing: The first mixture from Step 3) is fired at 890°C for 11 hours in an oxidizing atmosphere so as to obtain a first fired powder. Step 5) Wet bead milling: The first fired powder from Step 4) is bead milled with solid to water weight ratio of 6:4 for 20 minutes, followed by filtering, drying, and sieving process so as to obtain a milled powder.
Step 6) Second mixing: the milled powder from Step 5) is mixed with LiOH in an industrial blender so as to obtain a second mixture having a lithium to metal ratio of 0.99.
Step 7) Second firing: the second mixture from Step 6) is fired at 760°C for 10 hours in a oxidizing atmosphere, followed by crushing and sieving process so as to obtain a second fired powder labelled as CEX1.1.
Comparative Example 2
A single-crystalline positive electrode active material labelled as CEX2 is prepared according to the following steps:
Step 1) Transition metal oxidized hydroxide precursor preparation: A nickel-based transition metal oxidized hydroxide powder (TMH2) having a metal composition of Ni0.86Mn0.07Co0.07 is prepared by a co-precipitation process in a large-scale continuous stirred tank reactor (CSTR) with mixed nickel manganese cobalt sulfates, sodium hydroxide, and ammonia.
Step 2) Heating: the TMH2 prepared from Step 1) is heated at 400°C for 7 hours in an oxidizing atmosphere to obtain a heated powder.
Step 3) First mixing: the heated powder prepared from Step 2) is mixed with LiOH in an industrial blender so as to obtain a first mixture having a lithium to metal ratio of 0.96. Step 4) First firing: The first mixture from Step 3) is fired at 890°C for 11 hours in an oxidizing atmosphere so as to obtain a first fired powder.
Step 5) Wet bead milling: The first fired powder from Step 4) is bead milled in a solution containing 0.5 mol% Co with respect to the total molar contents of Ni, Mn, and Co in the first fired powder followed by dying and sieving process so as to obtain a milled powder. The bead milling solid to solution weight ratio is 6:4 and is conducted for 20 minutes.
Step 6) Second mixing: the milled powder obtained from Step 5) is mixed in an industrial blender with 1.5 mol% Co from CO3O4 and 7.5 mol% Li from LiOH, each with respect to the total molar contents of Ni, Mn, and Co in the milled powder so as to obtain a second mixture.
Step 7) Second firing: The second mixture from Step 6) is fired at 760°C for 10 hours in an oxidizing atmosphere followed by crushing and sieving process so as to obtain a second fired powder labelled as CEX2.
Example 1
EX1.0 is prepared according to the following process:
Step 1) CEX1.1 is mixed with WO3 powder to obtain a mixture contains about 0.45 wt.% of tungsten with respect to the total weight of the mixture. Step 2) Heating the mixture obtained from Step 1) in a furnace under the flow of an oxidizing atmosphere at 350°C for 10 hours.
Step 3) Crushing and sieving the heated product from Step 2) so as to obtain a powder labelled as EX1.0.
EX1.1 is prepared according to the following process:
Step 1) CEX2 is mixed with WO3 powder to obtain a mixture contains about 0.24 wt.% of tungsten with respect to the total weight of the mixture.
Step 2) Heating the mixture obtained from Step 1) in a furnace under the flow of an oxidizing atmosphere at 350°C for 10 hours.
Step 3) Crushing and sieving the heated product from Step 2) so as to obtain a powder labelled as EX1.1.
EX1.2, EX1.3, EX1.4, EX1.5, EX1.6, and EX1.7 are prepared according to the same method as EX1.1 except that in the Step 1) CEX2 is mixed with WO3 powder so as to obtain a mixture contains about 0.36, 0.43, 0.45, 0.48, 0.75, and 1.50 wt.% of tungsten with respect to the total weight of the mixture, respectively.
EX1.8 and EX1.9 are prepared according to the same method as EX1.1 except that in the Step 1) CEX2 is mixed with WO3 powder so as to obtain a mixture contains about 0.36 wt.% of tungsten with respect to the total weight of the mixture, and the heating temperature in the Step 2) are 300°C and 400°C, respectively.
Comparative Example 3
CEX3.1 is prepared according to the same method as EX1.1 except that in the Step 1) CEX2 is mixed with WO3 powder so as to obtain a mixture contains about 3.00 wt.% of tungsten with respect to the total weight of the mixture.
CEX3.2 is prepared according to the same method as EX1.1 except that in the Step 1) CEX2 is mixed with WO3 powder so as to obtain a mixture contains about 0.36 wt.% of tungsten with respect to the total weight of the mixture, and no heating is applied in the Step 2).
CEX3.3 is prepared according to the same method as EX1.1 except that in the Step 1) CEX2 is mixed with WO3 powder so as to obtain a mixture contains about 0.45 wt.% of tungsten with respect to the total weight of the mixture, and the heating temperature applied in the Step 2) is 550°C. The particle size distributions of the products from CEX1.1, CEX2, and EX1.3 were determined by a Malvern Mastersizer 3000, as described in section 1.2 above. These products all have a median particle size D50 of between 3.8 and 4.5 pm and D99 between 9.6 pm to 11.1 pm.
Comparative Example 4
A polycrystalline positive electrode active material labelled as CEX4.1 is prepared according to the following steps:
Step 1) Transition metal oxidized hydroxide precursor preparation: two transition metalbased oxidized hydroxide precursors, each labelled as TMH3 and TMH4, were prepared by a co-precipitation process in a large-scale continuous stirred tank reactor (CSTR) with mixed nickel-manganese-cobalt sulfates, sodium hydroxide, and ammonia. TMH3 D50 is around 10 pm and TMH4 D50 is around 4 pm, both with metal composition of Nio.65Mno.20Coo.15- Step 2) First mixing: TMH3 and TMH4 obtained from Step 1) are mixed with LiOH and ZrC>2 powders to obtain a first mixture. TMH3 and TMH4 powders are mixed in a 7:3 ratio by weight, the lithium to metal molar ratio is 1.03, and the Zr content in the mixture is 3700 ppm.
Step 3) First firing: The first mixture from Step 2) is fired at 870°C for 12 hours in an oxidizing atmosphere so as to obtain a first fired powder labelled as CEX4.1.
CEX4.2 is prepared according to the following process:
Step 1) CEX4.1 is mixed with WO3 powder to obtain a mixture contains about 0.45 wt.% of tungsten with respect to the total weight of the mixture.
Step 2) Heating the mixture obtained from Step 1) in a furnace under the flow of an oxidizing atmosphere at 400°C for 7 hours.
Step 3) Crushing and sieving the heated product from Step 2) so as to obtain a powder labelled as CEX4.2.
Comparative Example 5
A single-crystalline positive electrode active material labelled as CEX5 is prepared according to the following steps:
Step 1) Transition metal oxidized hydroxide precursor preparation: A nickel-based transition metal oxidized hydroxide powder (TMH5) having a metal composition of Nio.6sMno.20Coo.12 is prepared by a co-precipitation process in a large-scale continuous stirred tank reactor (CSTR) with mixed nickel manganese cobalt sulfates, sodium hydroxide, and ammonia. Step 2) First mixing: TMH5 prepared from Step 1) is mixed with LiOH in an industrial blender so as to obtain a first mixture having a lithium to metal ratio of 0.97. Step 4) First firing: The first mixture from Step 2) is fired at 920°C for 10 hours in an oxidizing atmosphere so as to obtain a first fired powder.
Step 5) Jet milling: The first fired powder from Step 4) is jet milled to obtain a milled powder labelled as CEX5.
Example 2
A single-crystalline positive electrode active material labelled as EX2 is prepared according to the following steps:
Step 1) CEX5 is mixed with WO3 powder to obtain a mixture contains about 0.45 wt.% of tungsten with respect to the total weight of the mixture.
Step 2) Heating the mixture obtained from Step 1) in a furnace under the flow of an oxidizing atmosphere at 350°C for 10 hours.
Step 3) Crushing and sieving the heated product from Step 2) so as to obtain a powder labelled as EX2.
Comparative Example 6
A polycrystalline positive electrode active material labelled as CEX6.1 is prepared according to the following steps:
Step 1) Transition metal oxidized hydroxide precursor preparation: A nickel-based transition metal oxidized hydroxide powder (TMH6) having a metal composition of Nio.soMno. Coo.io is prepared by a co-precipitation process in a large-scale continuous stirred tank reactor (CSTR) with mixed nickel manganese cobalt sulfates, sodium hydroxide, and ammonia.
Step 2) First heating: TMH6 prepared from Step 1) is heated at 375°C for 7 hours in an oxidizing atmosphere to obtain a heated TMH6.
Step 3) First mixing: heated TMH6 prepared from Step 2) is mixed with LiOH in an industrial blender so as to obtain a first mixture having a lithium to metal ratio of 1.00.
Step 4) Second heating: The first mixture from Step 3) is fired at 810°C for 12 hours in an oxidizing atmosphere followed by crushing and sieving process so as to obtain a fired powder labelled as CEX6.1.
CEX6.2 is prepared according to the following process:
Step 1) CEX6.1 is mixed with WO3 powder to obtain a mixture contains about 0.42 wt.% of tungsten with respect to the total weight of the mixture.
Step 2) Heating the mixture obtained from Step 1) in a furnace under the flow of an oxidizing atmosphere at 285°C for 8 hours.
Step 3) Crushing and sieving the heated product from Step 2) so as to obtain a powder labelled as CEX6.2. The chemical compositions of the products from the examples and comparative examples counterexamples were determined by ICP-OES and are given in Table 2, expressed as a fraction compared to the total of Co, Ni, Mn and W. Table 2 summarizes the composition of examples and comparative examples and their corresponding electrochemical properties. EX1.0 shows DQ1 improvement in comparison with CEX1.1 indicating tungsten mixing and heating application according to this invention is advantageous. Likewise, EX1.4 shows higher DQ1 in comparison with CEX2.
ble 2. Summary of the composition and the corresponding electrochemical properties of example and comparative examples.
Figure imgf000017_0001
*expressed as fraction of (Co+Ni+Mn+W)
** as determined by ICP-OES measurement, expressed as percentage compared to the total weight of the product.
*** as determined by XRD analysis
- : not applicable
EX1.1 to EX1.7 and CEX3.1 each comprises different tungsten content but with same heating temperature at 350°C. The concentration ranges from 0.26 wt.% at EX1.1 to 1.42 wt.% at EX1.7 is demonstrated to effectively achieve the objective of this invention. On the contrary, CEX3.1 comprising 2.92 wt.% tungsten decreases DQ1 to 196.7 mAh/g from bare CEX2 of 198.1 mAh/g.
EX1.8, EX1.9, CEX 3.2, and CEX3.3 show heating temperature effect to the positive electrode active material comprising tungsten source. The heating temperature from 300°C at EX1.8 to 400°C at EX1.9 is demonstrated to effectively achieve the objective of this invention. On the contrary, CEX3.2 with no heating and CEX3.3 with 550°C heating shows low DQ1 of 193.3 mAh/g and 186.5 mAh/g, respectively. This result indicates heating after tungsten mixing is essential given the temperature is lower than 550°C.
CEX4.1 and CEX4.2 are positive electrode active material with polycrystalline morphology comprising 65 mol% Ni. CEX4.2 is further comprising 0.45 wt.% tungsten, however, shows no improvement of DQ1 in comparison with CEX4.1. CEX6.1 and CEX6.2 are positive electrode active material with polycrystalline morphology comprising 80 mol% Ni wherein CEX6.2 further comprising 0.42 wt.% tungsten. Similarly, there is no improvement in DQ1 for CEX6.2 in comparison with CEX6.1. It is observed that the polycrystalline morphology is not suitable to achieve the improvement in the DQ1 even with higher total Ni content in the material. On the other hand, EX2 having a single-crystalline morphology comprising 68 mol% and 0.45 wt.% tungsten shows DQ1 improvement in comparison with CEX5 comprising the same Ni amount.
X-ray diffractometry is conducted to identify tungsten phases correspond to the heating temperature. Figure 1 shows the XRD patterns of EX1.7 has three phases: R-3m (a third compound phase of LiNi0.86Mn0.07Co0.07O2 according to this invention), R-3 (a first compound phase of U2WO4 according to this invention), and P21/n (a second compound phase of WO3).
Figure 2 shows the XRD patterns of CEX3.3, EX1.4, and CEX2. CEX2 and CEX3.3 have XRD patterns related to a R-3m phase. According to "Journal of Power Sources (2000), 90, 76- 81", the XRD patterns indicates that CEX2 and CEX3.3 are lithium transition metal oxide compounds. They have a general formula of LiNi0.86Mn0.07Co0.07O2. EX1.4 shows R-3m, R-3, and P21/n phases correspond to LiNi0.86 n0.07Co0.07O2, U2WO4, and WO3, respectively as described in Figure 1. This result indicates that 350°C heating temperature is suitable to produce the first and second compound phases according to this invention. It is when the aforementioned R-3m, R-3, and P21/n phases presence in the positive electrode active material, the electrochemical properties are improved.

Claims

1. A positive electrode active material for lithium-ion liquid electrolyte rechargeable batteries, whereby the positive electrode active material is a powder which comprises Li, M', and O, wherein M' consists of:
- Co in a content x superior or equal to 2.0 mol% and inferior or equal to 35.0 mol%, relative to M',
Mn in a content y superior or equal to 0 mol% and inferior or equal to 35.0 mol%, relative to M',
- A in a content m superior or equal to 0 mol% and inferior or equal to 5 mol%, relative to M', whereby A comprises at least one element of the group consisting of: Al, Ba, B, Mg, Nb, Sr, Ti, W, S, Ca, Cr, Zn, V, Y, Si, and Zr,
Ni in a content of 100-x-y-m mol%, i. a first compound which comprises U2WO4, ii. and a second compound which comprises WO3, whereby the powder is a single-crystalline powder, whereby the positive electrode active material comprises Li in a molar ratio of Li/(Co+Mn+Ni+A) of at least 0.900 and at most 1.100.
2. Positive electrode active material according to claim 1, whereby the positive electrode active material comprises a third compound which has a crystal structure which belongs to the R-3m space group.
3. Positive electrode active material according to claim 1 or 2, whereby the positive electrode active material comprises a third compound which is a Li-M'-oxide.
4. Positive electrode active material according to any of the previous claims, whereby said first compound has a crystal structure which belongs to the R-3 space group, and whereby said second compound has a crystal structure which belongs to the P21/n space group, as determined by X-Ray diffraction analysis.
5. Positive electrode active material according to any of claims 1 to 2, wherein the total content of tungsten is between 0.20 wt.% and 2.50 wt.% with respect to the total weight of said positive electrode active material, as determined by ICP-OES analysis.
6. Positive electrode active material according to any of the previous claims, wherein the total content of tungsten is between 0.30 wt.% and 2.00 wt.% with respect to the total weight of said positive electrode active material, as determined by ICP-OES analysis.
7. Positive electrode active material according to any of the previous claims, wherein the positive electrode active material has a median particle size D50 of between 2 pm and 7 pm, as determined by laser diffraction particle size analysis.
8. Positive electrode active material according to any of the previous claims, whereby the positive electrode active material size D99 is at least 5 pm and at most 25 pm, as determined by laser diffraction particle size analysis.
9. Positive electrode active material according to any of the previous claims, wherein the positive electrode active material size D99 is at least 7 pm and at most 20 pm, as determined by laser diffraction particle size analysis.
10. Positive electrode active material according to any of the previous claims, whereby m is inferior or equal to 2.0 mol%, relative to M'.
11. Positive electrode active material according to any of the previous claims, whereby the first compound is IJ2WO4.
12. Positive electrode active material according to any of the previous claims, whereby the second compound is WO3.
13. Positive electrode active material according to any of the previous claims, wherein Ni content 100-x-y-m is between 60 mol% to 95 mol%, relative to M'.
14. A lithium-ion rechargeable battery comprising a positive electrode active material according to any of the previous claims.
15. Battery cell comprising a positive electrode active material according to any of claims 1 to 13.
16. Use of a positive electrode active material according to any of claims 1 to 13 in a battery of either one of portable computer, a tablet, a mobile phone, an electrically powered vehicle, and an energy storage system.
PCT/EP2021/086400 2020-12-18 2021-12-17 A positive electrode active material for rechargeable lithium-ion batteries WO2022129473A1 (en)

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